Manufacture of oil and fat soluble azo dyestuffs



l at entecl Aug. 18, 1931 UNIT-ED STATES YPIATYE NT 4 ADOLF annsna AND nmvs'r WYSARD, or BASEL, swrr'z nRLA-ivn, AssIen'oRs ro "J. R. enrer s. A., or BASEL, S I ZERLAND MANUFACTURE OF OIL AND FAT SOLUBLE AZO DYESTUFFS No Drawing. Application filed November 23, 1928, Serial No. 321,514, andin Germany December 3; 1 927.

An ordinary oil and fat soluble azo dyestufi', such for example as meta-toluidine coupled with B-naphthol, when dissolved by grinding with boiled linseedoil varnish and 5 rolled upon paper, gives in lithographic works weak prints which dry up very slowly and dully and considerably wet through pa per. Additions of known drying substances, such as lead, manganese and cobalt compounds shorten the time of drying somewhat.

From systematic research on oil soluble dyestuiis it has now surprisingly been found that the solubility of ordinary fat dyestufi's in fat oils, as for example linseed oil. Varnish, is

greatly improved and thereby the drying property greatly increased in lithographic print works if two molecules of a fat dyestuff of the abovementioned kind are united together by means of a CHE-group, in which R represents hydrogen or a simple or substituted aryl radical.

Thus for example the dyestuit from the diamino base of a benzaldeliyde and meta-toluidine or para-xylidine, when tetrazotized and 5 aforesaid union of two dyestuff molecules could not have been foreseen, and is nowhere described. As dyestuffs all those are suitable which are obtained by coupling tetrazotized diaminodiphenylmethane and diaininotriphenylniethane bases and their derivatives with amines, phenols, pyrazolones or" their derivat ves and other usual *unsulphonated a z1o components, and which are soluble in fat 01 s.

shown in German patent specifications Nos. 11969 and 308785 or according to C 1908 (1) 1393.

The diamino bases of the diand triaryhnethane series are: easily obtained as It is advisable, especially if a dyestufl is not very easily soluble in fat'oils, to produce same "in the presence of; Turkey red oil' or other similarly acting substances,

The -following examples will serve to ex. plain the improved process.

Example p 6.6 kg. of the diamino basefrombenzaldehyde and para-xy1idine are tetrazotize d as usual and combined with a solution of 5.8 kg. of ,8-naphthol in 1.6 kg. of caustic soda lye of 100 per cent strength and 10 kg. of

sodium carbonate. The separated; dyestuif is filtered off, washed neutral and dried. The

red powder is soluble in concentrated sulphuric acid with a violet coloration.

The dyestuff has the "following structural formula:

Example 2 6.4 kg. of the diamino base of 94.6 per cent strength from benzaldehyde and ortho-toluidine are converted into the diazo body and its solution is poured into 4.5 kg. of paracresol in 1.6 kg. of caustic soda lye of 100 per cent strength 10 kg. of sodium carbonate and 50 gr. of Turkey red oil. When the cou- Example 3 5.5 kg. of the diamino base from orthochlorobenzaldehyde and para-xylidine are after tetrazotisation combined with 5.4 kg. of phenylmethylpyrazolone of 98 per cent strength dissolved in the necessary quantity of caustic soda lye and 8 kg. of sodium carbonate. The dyestuff isolated as usual is a dull yellow powder which gives a yellow solution in concentrated sulphuric acid.

The dyestufl has the following structural formula:

The same quantity of tetrazotized diamino base as in Example 3' is combined in acid medium with a watery solution of 3.7 5 kg. of meta-toluylenediamine of 99 per cent strength, is rendered after a short time alkaline with respect to litmus paper by means of sodium carbonate and worked up. The orange colored powder dissolves in concentrated sulphuric acid with an orange-yellow coloration. I

The dyestuff has the following structural formula:

(1H3 CH3 CH3 CH3 Example 5 3.43 kg. of the basefrom meta-toluidine and formaldehyde are tetrazotized as usual and coupled with 3.4 kg. of para-cresol, 1.2 kg. of caustic soda lye'of 100 per cent strength and 8 kg. of sodium carbonate. After a short time the product is filtered off and washed neutral. The yellow dyestuff has good drying properties in linseed oil, but shows only a moderate yield in printing.

The dyestuif has the following structural formula:

I N=N N=N-O C H 2 1 dlHa- CH3 Example 6' The diazo solution of Example 0 is combined with 3.7 5 kg. of meta-toluylenediamine as in Example 4:. An orangeyellow dyestufl' is obtained with similar properties as in Example 5. r

The dyestuff has formula:

(I311: i j i CH3 HzN I NH,

N=N\( /N=N I NHZ NH2 In the following table are given the properties of some dyestuffsobtained according to the improved process. There is a great range of alterations of the components which may be made on lines of this invention, both with respect to the aldehydes and to the bases and the coupling components.

the following structural Diamino base from Coupling component Shade of the print ag fig Aldehyde Amino Benzaldehyde Ortho-chloraniline Para-cresol Reddish yellow Very good. Benzaldehyde Ortho-chloraniline. fl-naphthol Good. Benzaldehyde Ortho-toluidine Para-cresol. Good. Ortho-chlcrobenzaldehyde Ortho-toluidine. Para-cresoL- Good. Benzaldchyde Ortho-toluidine. B-naphthol. Very good. Ortho-chlorobenzaldehyde. Ortho-toluidine. B-naphthol... Very good. Ortho-chlorobenzaldehyde. .i. Meta-toluidlne Para-cresol... Green-yellow Very good. Benzaldchyde Meta-toluidine Para-cresol... Green-yellow Very good. Benzaldchyde Meta toluidine B-naphthoL. Yellowish red- Very good. Ortho-chlorobenzaldehydc Meta-toluidine fl-naphthol Yellowlsh red. Very good. Ortho-chlorobenzaldehyde Para-xylidine Phenylmethyl-pyrazolone Yellow; Good. Ortho-chlorobcnzaldehyde Para-xylidine 2.3-otxynaphthoic acid ethyl- Bluish red Very good.

7 cs er. Ortho-chlorobenzaldehyde Para-xylidine Meta-toluylene diamine. Pure orange Very good. Ortho-chlorobenzaldehyde Para-xylidine 2.3-oxynaphtho1c acid Claret Fairly good. Ortho-ohlorobenzaldehyde Para-xy1idine Aceto-acetic ester Yellowish brown Very good. Para-xylidine. Para-cresol Yellow Very good. Para-xylidine Resorcine Fiery red brown Very good. Para-xylidlne. Oresidine Orange-yellow- Fairly good. Para-xylidine... B-naphthol Red- Very good. Para-xylidino. Para-crosoL'. Greenish yellow. Very good. Para-xylidine. Naphthol AS Very good. Para-xylidinc. B-naphthol Very good. Meta chlorobenzaldohyde Para-xylidine B-naphthol Very good. Para-chlorobenzaldehyde Para-xylidine. B naphthol Fawn-rod Good. Formaldehyde Meta-toluidine Para-cresol Reddish yellow. Good. Formaldehyde. Metaioluidine Meta-toluylene-diamm Good.

What we claim is 1. As new articles of manufacture, the herein described oil and fat soluble azo-dyestuffs for print works, obtained by coupling a tetrazotized diamino base from a benzalde hyde and para-Xylidine with unsulphonated azo components, said azo-dyestuffs being very easily soluble in linseed oil and having in oil solution the properties of well and rap idly drying up and not blotting.

2. As new articles of manufacture, the herein described oil and fat soluble azo-dyestuffs for print works, obtained by coupling a tetrazotized diamino base from a halogen substituted benzaldehyde and para-Xylidine with unsulphonated azo components, said azo-dystufls being very easily soluble in linseed oil and having in oilsolution the properties of well and rapidly drying up and not blotting.

3. As new articles of manufacture, the herein described oil and fat soluble azo-dyestufi's for print works, obtained by coupling a tetrazotized diamino base from an aldehyde and a primary amine of the benzene series with unsulphonated azo components said azo-dyestuffs being very easily soluble in linseed oil and having in oil solution the properties of well and rapidly drying up and not blotting.

4. As new articles of manufacture, the herein described oil and fat soluble azo-dyestuffs for print works, obtained by coupling a tetrazotized diamino base from an aldehyde and para-Xylidine with unsulphonated azo components, said azo-dyestulfs being very easily soluble in linseed oil and having in oil solution the properties of well and rapidly drying up and not blotting.

5. As new articles of manufacture, the herein described oil and fat soluble azo-dyestuffs for print works, obtained by coupling ADOLF KREBSER. ERNST WYSARD.

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